O2 Activation by a Heterobimetallic Zr/Co Complex
Abstract
Oxygen reduction is a critical half reaction in renewable fuel cell development and a key step in the development of aerobic oxidation reactions. We report rapid two-electron O2 reduction by a d0 ZrIV center with an appended redox-active Co–I site serving as an electron reservoir. The early/late heterobimetallic Zr/Co complex (THF)Zr(MesNPiPr2)3CoCNtBu (1) reacts readily with O2 and O atom transfer reagents to generate reactive oxygenated species including terminal peroxo and oxo complexes, (O2)Zr(MesNPiPr2)3CoCNtBu (2) and O≡Zr(MesNPiPr2)3CoCNtBu (3). The bimetallic Zr/Co complex provides a new cooperative synthetic pathway to promote multielectron redox processes such as oxygen reduction, with each metal playing a distinct role as a substrate binding site or redox mediator.
- Authors:
-
[1];
[1];
[2];
[2];
[1]
- The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
- Brandeis Univ., Waltham, MA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- The Ohio State Univ., Columbus, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1524776
- Grant/Contract Number:
- SC0019179
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 24; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhang, Hongtu, Hatzis, Gregory P., Moore, Curtis E., Dickie, Diane A., Bezpalko, Mark W., Foxman, Bruce M., and Thomas, Christine M. O2 Activation by a Heterobimetallic Zr/Co Complex. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b04215.
Zhang, Hongtu, Hatzis, Gregory P., Moore, Curtis E., Dickie, Diane A., Bezpalko, Mark W., Foxman, Bruce M., & Thomas, Christine M. O2 Activation by a Heterobimetallic Zr/Co Complex. United States. https://doi.org/10.1021/jacs.9b04215
Zhang, Hongtu, Hatzis, Gregory P., Moore, Curtis E., Dickie, Diane A., Bezpalko, Mark W., Foxman, Bruce M., and Thomas, Christine M. Mon .
"O2 Activation by a Heterobimetallic Zr/Co Complex". United States. https://doi.org/10.1021/jacs.9b04215. https://www.osti.gov/servlets/purl/1524776.
@article{osti_1524776,
title = {O2 Activation by a Heterobimetallic Zr/Co Complex},
author = {Zhang, Hongtu and Hatzis, Gregory P. and Moore, Curtis E. and Dickie, Diane A. and Bezpalko, Mark W. and Foxman, Bruce M. and Thomas, Christine M.},
abstractNote = {Oxygen reduction is a critical half reaction in renewable fuel cell development and a key step in the development of aerobic oxidation reactions. We report rapid two-electron O2 reduction by a d0 ZrIV center with an appended redox-active Co–I site serving as an electron reservoir. The early/late heterobimetallic Zr/Co complex (THF)Zr(MesNPiPr2)3CoCNtBu (1) reacts readily with O2 and O atom transfer reagents to generate reactive oxygenated species including terminal peroxo and oxo complexes, (O2)Zr(MesNPiPr2)3CoCNtBu (2) and O≡Zr(MesNPiPr2)3CoCNtBu (3). The bimetallic Zr/Co complex provides a new cooperative synthetic pathway to promote multielectron redox processes such as oxygen reduction, with each metal playing a distinct role as a substrate binding site or redox mediator.},
doi = {10.1021/jacs.9b04215},
journal = {Journal of the American Chemical Society},
number = 24,
volume = 141,
place = {United States},
year = {Mon Jun 03 00:00:00 EDT 2019},
month = {Mon Jun 03 00:00:00 EDT 2019}
}
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